Art of coloring



ence of a tertiary base.

Patented Jan. 24, 1933 4 UNITED STATES PATENT OFFILCE RONALD SIDNEY BARNES, OF GRANGEMOUTH, DUNCAN SERVICE, OF FALK IBK, AND

JOHN THOMAS, OF POLMONT, SCOTLAND, ASSIGNORS TO SCOTTISH DYES LIMITED, v

A CORPORATION OF GREAT BRITAIN ART OF COLORING by dyeing from a bath containing the ester .along with aluminium sulphate and-calcium acetate, and then steaming. In this way the alizarine is obtained on the fibre as a mordant color by a much simpler process than the usual one in which alizarine itself is applied. to the previously mordanted fibre. This is a matter of considerable importance, particularly when carried out on a practical or large scale, and the invention is regarded as having a broad basis.

The invention in brief consists in the process in the art of mordant coloring which comprises the application of a soluble ester of a mordant d 'estufi along with the mordant,

followed a r impregnation by a hydrolytic treatment, for example, steaming,

The invention also consists in a process according to which esters are prepared by treating alizarine with the sulphur trioxides of pyridine or other tertiary bases or substances capable of producing such trioxides, the treatment being carried out in the pres- The invention also consists in a process according to either of the preceding two paragraphs applied to esters of alizarine and esters of alizarines generally, as well as other mordant dyestufis, v

I The invention also consists in a process according to either of the preceding three paragraphs or substantially. as described for the 1 production of the disulphuric ester of alizarine. 'l

-.1l'o Drawing. Application flled'Har'ch 26, 1981, Serial No. 525,600, and in Great Britain Kai-ch 31, 1930.

The invention also consists in a process which comprises the utilization of sulphuric estersof alizarine (in which the sulphuric ester is attached to the b-hydroxy group) in the art of coloring by dyeing from a bath containing the ester, with aluminium sulphate and calcium acetate, and then steaming.

The invention also consists in methods for the production of starting esters, such as may be used in the processes of any of the preceding five paragraphs, substantially as described.

The invention also consists in processes The following examples illustrate how the invention may be carried into efiect, references to parts and to percentages being to parts and percentages by weight, and refer ence to pressure being to pressure in pounds per square inch above atmosphere.

Ewamp lel '15 parts of alizarine, 100 parts of pyridine and 50 parts pyridine sulphur trioxide are stirred together and heat-ed to 75 C. After stirring for about 15 to 30 minutes, the whole is allowed to cool, and the product filtered off.

This is obtained in the form of the pyridine 'salt of the ester.

Example 2% This is an example'of the use of the ester for the production of alizarine red shades on cotton. .The ester is dissolved in a solution containing 10% of crystalline aluminium sulphate Al (SO 18H O and 1% of calcium acetate calculated on the volume of the liquor.

The cotton is then entered and dyed for 30 minutes at 60 C. It is removed from the dyeing bath and rinsed in water, impregnated with soluble oil, and then dried, and steamed for one hour at 15 lbs. pressure.

Example 3 Thisin an example of printing cotton with alizarine ester. The printing paste is made up as follows 1, Parts Alizarine ester 25% paste 5.0- British gum 13.7 Acetic acid 9 Tw 1.0 Aluminium sulphocyanide 5.0 Calcium acetate 23 Tw 0.3

The constituents being added in the order 'ven are rinted on the cloth which is then riedon the hot roller, steamed for 30 minutes at 15 lbs. pressure, boiled for 10 minutes in 0.5% soap solution.

I sample This is similar to Example 3 but 0.5 part of the British gum in the printin paste are replaced by equal quantity of 20 q soluble oil.

7 Example 5 This is an example of the use of alizarine ester on natural silk.

1 part of 25% ester paste is dissolved in 200 parts of 1% solution of aluminium sulphate. The silk is-then entered cold and the ath gradually taken up to the boil, and then whileboilin'g for a further of an hour 5 parts of a 10% solution of calcium acetate gradually added. The silk is then removed, rinsed in a 1%. sodium arsenate solution at C. for 10 minutes, soaped for an hour in a boiling 1% soap bath, rinsed and dried.

Example 6 This is an example of the production of the disulphuric ester of alizarine.

10 parts of alizarine in he form of a dr powder, 100 parts of pyridine sulphur tr1- oxide and 10 parts of pyridine are heated together at 110 C. for. two hours when the melt becomes almost solid, 50 cc. of yridine are stirredin and the mixture allowe to cool;

v the solid is filtered off, and washed with water until the filtrates are acid free.

The product is a disulphuric acid ester of alizarlne.

Example 7 1 This is an example of the dyeing of disulphuric ester on cotton.

The ester is dissolved in a solution containilllg 5 parts 1'p1er100 of crystalline aluminium s phate. e cotton is entered cold,'and the whole ually taken up to 100 C. during an our; 9. further boiling is given for of an hour'during which time 5 parts of calcium acetate are adually added. -The dyed goods are then lifted from the bath and solution of calcium acetate.

w orked for 10 minutes in a 2% solution of sodium arsenate at 60 C. This is followed by immersion in a 10% solution of soluble 011 for 10 minutes. The treated material is then removed and steamed for V an hour to 1 hour at 15 lbs. pressure, soaped and dried.

. Example 8 This comprises the substitution for alizarine esters referred to in previous examples of other alizarine esters for instance the ester of 1.2.6. trihydroxy-anthraq'uinone. 1:2: 6-

. trih droxy-anthraquinone is Flavopurpurine Color Index No. 1039.

, Example 9 (Allzarine This is an example of the application of the ester of alizarine to wool on a chrome mordant. 10 parts-of the woolen material are mordanted with 200 parts of a solution containing 0.3 parts of potassium bichromate Example 10 This is an example of the application of the alizarine ester on wool by the top-chrome method. The dye bath is made up with a requisite quantity of the dyestufi in 600 parts of water. The wool is then entered at 80 C. taken to the boil and boiled for 45 minutes durin which time 5 parts of 5% acetic acid and then 2 parts of 5% sulphuric acid are gradually added. 2 parts of 10% calcium y acetate solution are then added and boiled for a further 15 minutes, when 25 parts of 1% potassium bichromate solution are added 'and the whole boiled for a further hour.

Example 11 the alizarine ester on wool by the metachrome method. The requisite quantity of I This'is an example of the application of the alizarine ester is dissolved in 600 parts of water with 0.2' parts of potassium chro mate, 0.1 part of ammonium sul hate and 2 arts of a 10% solution of calcium acetate.

he temperature is taken to 80 C. and the substances thoroughly mixed and dissolved. The material is now entered and-the whole raised to the boil, a vi orous boil is then 'ven for .1 to 2 hours until the requisite shade is obtained.

This example like Numbers 9. and 10 've fast shades, slightly duller and redder an alizarine itself, and the methods are suitable for use in circulating machines.

' Example L2 20 parts of alizarine ester 75 parts of a 10% solution of aluminium sulphate (Al S0 18H O) Parts Sodium carbonate 40 Sodium hydrogen phosphate 35 Calcium chloride (caCl fiH O) 6O Soluble oil 50 Al (SO .18H O -i 50 The mixture is then taken up to the boil in 30 minutes, boiled for 1 hour and another 10 parts of sodium carbonate solution added.

Ewample '13 This is another example of the application of the ester of alizarine on cotton, the ester being applied this time to mordanted cotton. The requisite quantity of soluble alizarine ester is entered into a bath containing 195 parts of water, 2 parts of calcium chloride and 5 Parts of 5% acetic acid. The cotton previously mordanted with calcium and aluminium, is entered into the above bath at 80 C. taken to the boil and boiled vigorously for 2 hours, after which it is removed and soaped or oiled and steamed in the usual manner.

Example 14 This is an example of the application of the sulphuric ester from Alizarine brown WLS. This ester being dyed from a chrome mordant on wool. The material, previously mordanted by the usual treatment, in a bath containing 3% potassium bichromate and 1% of sulphuric acid calculated on the weight of the material, is entered at 80 into a bath containing the soluble alizarine ester. The temperature is raised to the boil, and exhaustion obtained by the addition of 5% sulphuric acid. The acid is added during the first hours boil and the dyeing is then continued for a further hour.

An alternative chrome mordant cloth which can be used is that prepared with potassium bichromate using potassium tartrate in, lieu of sulphuric acid Alizarine brown from stage.

WLS is identified in Color index as No. 1035.

Example 15 This is a similar a plication to Example 14, except that an a -chrome method is employed. The dye, bath is made up by dissolvin the requisite quantity of the ester izarine brown WLS in 600 parts of water, 10 parts of wool material are then entered at 80 C. The temperature raised to the boil and then 2 parts of concentrated lactic acid gradually added over a period of 1 hour, after which 30 parts of 1% potassium bichromate solution are added and the whole boiled for a further hour.

General We repeat that the invention is regarded as of broad aspect. It is not limited to esters of alizarine but includes esters of alizarines generally, that is the other 1.2-dihydroxyanthraquinone derivatives and other mordant dyestuffs. I

The invention deals with manufacture, for example the manufacture, of certain esters and also with use, namely the use ofproducts which may be made according to the processes described or indicated whether made by those processes or not. In connection with use, it is pointed out that it is not necessary for the material to be first mordanted in a separate Particular attention is drawn to the production of the disulphuric ester of alizarine.

The invention is not limited to any particular theory, but it appearsthat the hydroxy groups which are esterified in thealizarine .by processes such as referred to above are the groups in the 1- and 2-positions. As many apparently widely difierent embodiments of this invention may be made without departing from the spiritand scope thereof, it is to be understood that we donot limit ourselves to the specific embodiments thereof except as defined in the appended claims;

' We claim:

1. Process for the production of dyeings (including printings) on textile materials,'

which comprises applying to the material, a soluble sulphuric ester of an anthraquinone body having at least two hydroxyl groups, two hydroxyl groups being in adjacent a-and B-positions, and at least the fi-hydroxylgroup being sulphated.

2. Process for the production of dyeings (including printings) on textile materials,

which comprises applying to the material, a sulphuric ester of ali'zarine in'which at least the B-hydroxyl group is sulphated.

3. Process according to claim lin which the sulphuric ester is applied to the material in the presence of a mordant.

4. Process according to claim 2'in which material in the presence of a mordant.

5. Process according to claim 1 followed by the application of a mordant.

6. Process according to claim 2 followed by the application of a mordant.

7. Process according to claim 1 in which the sulphuric ester is applied to the material together with a. mordant the application being followed by steaming.

8. Process according to claim 2 in which the alizarine sulphuric ester is applied to the material together with a mordant, the application being followed by steaming.

9. Process for the production of dyeings (including printings) on textile materials which comprises applying to the material an alizarine sulphuric ester (in which at least a the ,B-hydroxyl group is sulphated) aluminium sulphate and calcium acetate, and subsequently steaming.

10. In the manufacture of mordant-dyed textile materials, the process which comprises impregnating the said materials with a betasulphuric ester of alizarine and a soluble salt capable of functioning as a mordant and su sequently submitting the impregnated material to a hydroltic treatment to produce said mordant-dyed textile materials.

11. In the manufacture of mordant-dyed textile materials, the process which comprises dine salt of beta-sulphuric ester of alizarine and a soluble salt capable of functioning as a mordant and subsequently submitting the impregnated material to a hydrolitic treatment to produce said mordant-dyed textile ma terials.

14. In the manufacture of mordant-dyed text le materials, the process which comprises impregnating the said materials with a composition comprising a pyridine salt ofbetasulphuric ester of alizarine, a soluble salt of aluminium and a soluble salt of calcium and subsequently steaming the impregnated material.

.textile materials, the step which comprises applying to textile materials an anthraquinthe alizarine sulphuric ester is applied to the one dyestufi containing within the molecule the following characteristic structure:

wherein X represents a hydroxy ester group;

17 The process of claim 16 wherein the application of the said anthraquinone dyestuif is effected in the presence of a mordant.

18. The process of claim 16 wherein the said textile material is a mordant impregnafed textile material.

19. The process of claim 16 wherein a mordant is simultaneously applied with said anthraquinone dyestufl'.

20. The process of claim 16 wherein the said anthraquinone dyestutf is a disulphuric ester.

21. The process of claim 16 wherein said anthraquinone compound is a beta-sulphuric ester. of alpha-beta-dihydroxy anthraquinone.

22. In the manufacture of mordant-dyed or sulphuric textile material, the process which comprises i printing a textile material with a printing paste comprising 'a beta-sulphuric ester of alizarine, an aluminium salt and calcium acetate,'dry1ng the printed textile material and then steaming the dried material.

23. In the manufacture of mordant-dyed textile materials, the step which comprises applying to textile @materials an anthraquipone dyestuif having the probable formu a:

osom wherein R represents an anthraquinone nucleus and Y represents hydrogen or a hydroxy group, the said QSO II group. being in a beta position.

24. The process of claim 23 in which the said textile material is cotton.

' said textile material is silk.

26. The process of claim 23 in which the said textile material is wool.

27. In the manufacture of mordant-dyed textile material, the step which comprises applying to the textile material an aqueous solution comprisin aluminium sulphate and an anthraqumone yestulf,\having the prob able formula:

a on H5 osodl wherein R represents an anthraquinone nucleus and Y represents h drogen or a hydroxy group, the said 0 0,11 group being in a beta position.

.28. The process of claim 23 in which the said textile material is mord'anted cotton.

29. In the manufacture of mordant-dyed textile material, the process which comprises immersing cotton mordanted with calcium and aluminum, in an aqueous bath compris- 5 ing calcium chloride, acetic acid and a beta sulphuric ester of alizarine in soluble form, heating the bath while the mordanted cotton is immersed therein, removing the cotton from the bath and subsequently steaming 1 the so-treated cotton.

- 30. In the manufacture of mordant-dyed textile material, the step which comprises applying to the textile material a beta-sulphuric ester of an alizarine dyestufl'.

1 31. The process of claim 30 in which a mordant is subsequently applied.

32. In the manufacture of mordant-dyed textile material, the process which comprises immersing wool in an aqueous solution comprising a beta-sulphuric ester of an alizarine dye, heating the solution to boiling while the wool is immersed therein, gradually adding acetic acid and sulphuric acid and then adding calcium acetate solution, the looiling being continued during suph addition, and finally addin potassium bichromate solution and comp eting the boiling to obtain the desired shade. I

33. In the manufacture of mordant-dyed textile material, the step which comprises applying to the textile material an aqueous solution comprising aluminum sulphate and a beta-sulphuric ester of an alizarlne dye.

34. The process of claim 16 in. which said sulphuric ester is a disulphuric ester.

35. In the manufacture of mordant-dyed textile material, the process which comprises. immersing cotton in an aqueous dye hath comprising an aluminum sulphate and a di- 40 sulphuric ester of an alizarine dyestufi, gradually heating the dye bath to boiling while the cottom is immersed therein, continuing the boiling and adding a solution of calcium acetate, removing the so-treated cotton from the bath and working in a solution of sodium arsenate at about 60 G, and subsequently steaming the so-treated cotton at about 15 pounds pressure and finally soaping and drying.

36, The process of claim 16 wherein two mordants are used to produce the desired shade.

In testimony whereof we afiix our signatures.

RONALD SIDNEY mares.

' DUNCAN SERVICE.

J. moms. 

